Material surface treatment method using concurrent electrical and photonic stimulation

ABSTRACT

A material surface treatment protocol (e.g., FIG.  13 ) uses concurrent electronic and photonic stimulation to generate an exothermic reaction and coat the surface (e.g., FIGS.  8  and  9 ) of a material, such as palladium. This protocol is performed at or near the boiling point of water within a sealed vessel that prevents the escape of steam and that is lined with silica or a similar glass to increase the silica available to the reaction. The great majority of the applied energy is heat used to elevate the temperature to near the boiling point, while concurrent stimulations provide only about 100 mW of additional energy for the surface treatment.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of U.S. patent application Ser. No.12/688,630, filed Jan. 15, 2010.

TECHNICAL FIELD

The invention relates to surface treatment of materials, and inparticular to preparation of the surface of a material in a liquidmedium in order to facilitate certain desirable exothermic reactionsusing 1-5 such material.

BACKGROUND ART

U.S. Pat. No. 7,442,287 describes a surface treatment method ofpreparing materials, such as palladium, at or near their surfaces inorder to facilitate their use, e.g., for generating exothermicreactions. In that treatment method, a solution in water of anelectrolyte, a surfactant, and a pH-adjusting agent (to maintain the pHof the solution between 6.5 and 8.9) is heated to and maintained at orjust below the boiling point in an open glass beaker. A pair ofelectrodes, at least one of which has the surface to be treated, isimmersed in the solution with a gap between them. The electrodes arethen electrically (and vibrationally) stimulated as a series of pulses,while simultaneously being photonically stimulated by a light source.Scanning electron microscope (SEM) images of the treated electrodes showthat the concurrent stimulations of the electrode material whileimmersed in the hot solution leave a silica coating with a stratifiedand sponge-like texture and in some instances form crater sites on theelectrode surface.

The metallic surface treated by the method provides enhanced sites forfacilitating desired reactions, e.g., hydrogen absorption and release,hydrogenation, catalytic reactions, and exothermic reactions. Palladium,e.g., is known to have a large capacity for hydrogen storage andrelease, useful for fuel cells and the like, the level of performance ofwhich depends on the presence of certain surface sites for efficienthydrogen exchange.

SUMMARY DISCLOSURE

The present invention is an improvement of our previous method set forthin the aforementioned '287 patent. Similar to before, the protocolconsists of a specific series of steps applying electrical and photonicstimuli between conductive electrodes immersed in a solution maintainedat an elevated temperature at or near the boiling point. In the presentprotocol, the solution includes a lithium silicate and is heated towithin 5° C. of the solution's boiling point (as defined for standardatmospheric pressure).

As the work on the protocol described in our previous patent hasprogressed, we have moved it from an open glass beaker into a sealedreactor to prevent the escape of steam, along with other constituents inthe solution or reaction products. As higher temperature boiling pointswere obtained under pressure, the treatment protocol proved to be morerobust when taking place in such a sealed container with specificrefinements.

Having the treatment reactions occur in the presence of silicaceousmaterial proved to be very beneficial. In particular, we obtained betterresults (1) when we lined the inner surface of the reaction reactor witha glass beaker, (2) when we put a quartz cap over the beaker, (3) whenwe replaced our stainless-steel thermocouple wells with glass ones, (4)when we threaded glass beads onto the electrodes, and (5) the solutioncontained either a soluble form of silica or a silica compound insuspension. When conducted in such a glass reactor, the use of a DCstimulus and a vibrational stimulus in the protocol proved to beoptional.

The electrode material immersed in the hot solution is subject toelectrical and photonic stimulation. It has been found that thetreatment works better when some RF frequencies are used as electricalstimuli than others, indicating a possible resonance phenomenon that hasproved to be beneficial. Stimulating the system at one or more resonantfrequencies can cause the underlying oscillation to amplify. Inparticular, an effective RF electrical stimulus was shown to be anamplified replication of a signal emitted during the reaction, which wasa 43.4 MHz sine wave added to a 3.1 MHz sine wave.

Temperature spikes were observed with electrodes made of four differentmetals: palladium, silver, platinum, and gold, and using differentsilica compounds: Mega H-™, Super Hydrate™, lithium metasilicate, sodiummetasilicate, and octamethylcyclotetrasiloxane.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a data log for a first experiment using a palladium electrodein a predominately heavy water (99.9% D₂O) solution and being stimulatedin accord with the method of the present invention.

FIG. 2 is an SEM images of an electrode surface resulting from treatmentby the protocol recorded in FIG. 1.

FIGS. 3, 4, and 5 are respective Energy Dispersive Spectrometry (EDS)spectral analyses of the deposited layer and bare metal for the treatedelectrode surface and of the cross-sectioned electrode.

FIGS. 6, 7, and 8 are SEM images of the cross-sectioned treatedelectrode surface (6 and 7) and of the electrode metal itself (8).

FIGS. 9 and 10 are EDS spectral analyses of the sectioned electrodemetal.

FIG. 11 is a data log for a replication of the test protocol, using apalladium electrode in a solution of anionic silica hydride and lithiumsulfate in predominately heavy water, and stimulated with a modulatedpulse stream.

FIG. 12 is a table of atomic concentrations for the electrode obtainedfrom Auger analysis after conclusion of the protocols for FIGS. 3-10.

FIG. 13 is a data log for a replication of the test protocol, againusing a palladium electrode in a predominately heavy water solution andstimulated in accord with the present invention.

FIG. 14 is an EDS spectral analysis of the electrode resulting from theprotocol for FIG. 13.

FIGS. 15, 16, and 17 are respective data log, and SEM photos of twopieces of the electrode from another experiment using glass beadsthreaded over palladium electrodes in a predominately heavy watersolution and stimulated in accord with the present invention.

FIG. 18 is a data log for yet another experiment conducted usingglass-bead-threaded palladium electrodes, but in a predominately lightwater solution and stimulated in accord with the present invention.

FIGS. 19 and 20 are data logs for experiments of the surface treatmentmethod respectively using silver and platinum electrodes inpredominately heavy water.

FIGS. 21 and 22 are data logs for experiments of the surface treatmentmethod, using palladium electrodes in heavy water, wherein lithiummetasilicate and sodium silicate, respectively, were dissolved in thesolution.

FIG. 23 is an SEM photo and accompanying EDS spectrum for the electroderesulting from the experiment corresponding to FIG. 22.

FIG. 24 is a data log for an experiment using a palladium electrode in asolution of lithium metasilicate and lithium sulfate in heavy water, andstimulated with a modulated pulse stream.

FIG. 25 is a data log for an experiment using a palladium electrode in asolution of lithium metasilicate and lithium sulfate in heavy water, andstimulated with a 3.1 MHz sine wave added to a 43.4 MHz sine wave.

FIG. 26 is a SEM image of an electrode used in that experiment.

FIG. 27 is a data log for an experiment using a palladium electrode in asolution of lithium silicate and a siloxane in heavy water, andstimulated with a simultaneous time-varying electrical and photonicsignal.

DETAILED DESCRIPTION

The treatment protocol is performed in an electrolytic cell consistingof two or more electrodes, composed of similar or dissimilar metals, forexample of palladium, silver, platinum, or gold, or even conductivematerial other than metal. One or more of the electrodes have materialsurfaces to be treated. At least one of the electrodes is in intimatecontact with a source of silicaceous material, and thus, for example,may be coated with silica or a silicate, threaded with silica or glassbeads, or the electrode may consist of sintered metal and silica. Theelectrodes are immersed in a solution or suspension of an electrolyte ina liquid, such as predominately heavy water (D₂O), lithium sulfate(Li₂SO₄), and a silica compound either in solution or in suspension. Wesay “predominately heavy water” when Flanagan's “Super Hydrate™” is usedin the protocol since it is made with light water. The drawing legendsshould be understood in that sense, since they say “heavy water” in theinterest of brevity. Alternatively, less active results have also beenobserved using predominately light water (H₂O). We say “predominatelylight, water” since our citric acid solution was made with heavy water.Again, the drawing legends should be understood in that sense, sincethey say “light water” in the interest of brevity. Thus, combinations ofboth light and heavy water have been used. A pH-buffering agent, as usedin our aforementioned '287 patent, was found to be optional. Thebuffering agent might comprise either EDTA, citric acid, sodiumbicarbonate, or lithium hydroxide in quantities sufficient when neededto maintain a pH in a range from 6.5 to 8.9.

As before, the electrolytic cell may be of any size needed toaccommodate a work piece whose surface is to be treated by thisprotocol. However, the reactor now used in the present invention was astainless steel cylinder with a central well 5.08 cm deep and 5.08 cm indiameter, having a closed bottom and a removable top. Ultimately, it wasdimensioned to accommodate a glass beaker capped with a quartz top.Alternatively, the reactor may be a glass- or silica-lined metallicreactor. The reactor could also be lined with a piezoelectric material,in the form, e.g., of a porcelain glaze. A sealed reactor prevented theescape of steam or very slight escape of steam, along with otherconstituents in the solution or reaction products, and allowed highertemperatures to be obtained under pressure for a given aqueous solution.The sealed reactor also made it much more practical to instrument theexperiments and to data log their results. Ports in the top allowedelectrodes and thermocouples to pass through it, while sealed glassports in the reactor wall allowed for the concurrent photonicstimulation by exterior illumination. The reactor weighed more than fivekilograms, thereby providing considerable thermal mass to ensure thatmeasured temperature transients were generated within the reactor andnot the result of external impulses. As a safety practice appropriatewhen working with exothermic reactions in a sealed reactor at or nearthe boiling point of water, our reactor was equipped with a pair ofpressure relief valves set to lift sequentially at different pressures.

An embodiment of the surface treatment method in accord with the presentinvention uses either of two commercial products called “Mega H-™” and“Super Hydrate™”, which are believed to be one source of silica withwhich the electrodes to be treated are in intimate contact. Thesecompositions are respectively the powdered and dissolved form of ananionic silica hydride, with additives. The following points can be madeabout these two products: They are described in their marketingliterature as 1) an anionic hydride organosiloxane; 2) a silsequioxanehaving hydroxyl-terminated constituents; 3) sources of ionized hydrogencontained within soluble microclusters of silica hydride; and 4)consisting of tetrahedral frameworks that encapsulate hydrogen anions.Pure samples of the products without additives were not available.According to its package label, Mega H-™ has potassium citrate,potassium carbonate, and oleic acid added. Super Hydrate™ has potassiumcarbonate, magnesium sulfate, and oleic acid added.

Alternative embodiments of the surface treatment method in accord withthe present invention have as sources of silica either sodiummetasilicate Na₂SiO₃ in solution, lithium metasilicate Li₂SiO₃ insuspension. A chelating agent, such as EDTA, may be used to facilitatethe suspension of the silica compound.

An additional alternative embodiment of the surface treatment method inaccord with the present invention has as a source of silica eitheroctamethyl-cyclotetrasiloxane or decamethylcyclopentasiloxane.

The liquid within the reactor was blanketed during the experiments withone or a combination of hydrogen and helium gases, for example inapproximately equal percentages, which were introduced through two inletvalves. The atmosphere was vented through an outlet valve. Thesaturation of the liquid with these gases is optional.

A heating coil was located in a cavity in the bottom of the reactor, andits input voltage and current measured to monitor input power. Thetemperature of the reactor was first raised to 102° C.±1°, thenmaintained until the temperature of the liquid had remained stable nearthe boiling point over an hour or more to establish a thermalequilibrium. A pair of thermocouples monitored the temperature of theliquid via thermocouple wells projecting into the liquid. The wells werefirst made of stainless steel and later of glass, which is preferred.The thermocouples also passed through the ports in the reactor's cap viaTeflon® seals compressed with Swagelok® fittings.

Through experimentation, it was determined over time that the exothermicreaction had a characteristic and readily identifiable temperatureresponse. In later experiments, there was less concern aboutestablishing steady temperature and the reactor was driven more quicklyto the operating range of the reaction and the stimuli were appliedsooner. No attempt was made to make calorimetric measurements due to thedifficulty of making such measurements near the phase change of aboiling liquid; the temperature transients were judged to be sufficientevidence of heat generation.

Two or more electrodes were immersed in the liquid. The work piece orpieces to be treated are used as one or more of these electrodes, whichcan be of any shape and size, such as that of a nozzle. The materialbeing surface treated by this method may be a conductive material suchas a solid metal or alloy, containing for example palladium, or may bemetallically plated with the desired surface material. Any of theelectrodes may also be surface coated with other materials, such assilicates, with either the underlying metal or the coating or both to betreated by the protocol.

RF electrical and photonic stimuli were applied in manner similar tothat previously described in our earlier patent. For example, in some ofour experiments, the electrical stimuli were provided via threepalladium electrodes of 0.063 mm diameter: an anode for the RF stimulus,a second anode for the DC stimulus, and a common cathode. The electrodeswere parallel and formed a triangle with sides 2.3, 3.7, and 3.7 cmlong. The shortest side lay between the RF anode and the common cathode.The electrical stimulation may, therefore, consist of either or bothdirect current and alternating current, where the alternating currentcan be modulated with frequencies in the RF range, preferably includingfrequencies that coincide with absorptive spectra of components of thesolution. The electrical stimulation may be a combination of directcurrent voltage and alternating current voltage applied, eitherconcurrently or sequentially, between either separate anodes or a commonanode and a common cathode. The electrodes and the thermocouples wereequally spaced on a bolt circle, so thermocouples would be 2.3 and 3.7cm away from the cathode. All electrodes were isolated from the reactorand sheathed in glass tubing to the surface of the liquid in order tokeep them straight and to concentrate the RF stimulus in the liquid. Theelectrodes passed through the reactor's top via Teflon® seals compressedwith Swagelok® fittings.

Four “Ultrabright” white light-emitting diodes (LEDs) capable ofgenerating 15,000 mcd were spaced equally around the reactor below thesurface of the liquid as photonic stimuli. These stimuli were providedthrough sealed glass ports in the reactor wall. The LEDs arepulse-modulated between their on and off states during the same periodwhen the electrical stimulation is applied. Electrical and photonicstimulation may be applied either concurrently or sequentially.

Having the treatment reactions occur in the presence of silica or glassproved to be very beneficial. Attempts to run the protocol withinreactors of stainless steel and Teflon® were not successful, even withsilicates added. We obtained better results (1) when we lined the innersurface of the reaction reactor with a glass beaker, (2) when we put aquartz cap over the beaker, (3) when we replaced our stainless-steelthermocouple wells with glass ones, and (4) when we threaded glass beadsonto the palladium electrodes. When conducted in such a glass reactor,the use of a DC stimulus in the protocol proved to be optional. Whenonly the AC stimulus was used, the word “cathode” is used to describethe grounded side of the AC signal. The AC stimulus was applied acrossthe two closest electrodes, i.e., those that were 2.3 cm apart.

Additionally, our solution contained a form of silica. We had noted thatthe first step in the protocol described in our earlier patent consistedof heating the solution until the bubbles had cleared from its surface.Those bubbles, of course, were characteristic of surfactants, and theMega H-™ and Super Hydrate™ had originally been chosen for theirreported surfactant properties.

The protocol typically requires at least two hours of treatment beforebursts of heat are observed. It is suspected that something must behappening to either the solution or to the electrodes in that period tofacilitate the observed reaction. Lithium salts, such as lithium sulfate(Li₂SO₄), are used as an electrolyte in the solution. Since the reactiondoes not occur immediately, it is possible that the silica and thelithium in our protocol are bonding in some way before the bursts ofheat are observed. In particular, the lithium may be combining with thesilica compound in the solution over the time frame of the treatmentprotocol to form a lithium silicate, possibly Li₂SiO₃ (lithiummetasilicate). Alternatively, since silsesquioxanes were used in theanionic silica hydride in the solution for the experiments, perhaps thelithium is either bonding to resulting siliceous cage structures orentering the center of the silica cage when that compound is used as thesource of the silica.

Octamethylcyclotetrasiloxane has a silica ring structure of four siliconatoms alternating with four oxygen atoms. It is known that lithium ionsbonds with the octamethylcyclotetrasiloxane, entering and leaving thecenter of the ring in a dynamic process that reaches a stochasticequilibrium over time. (For example, see: Ritch, J. S., Chivers T.;Angew. Chem. Int. Ed. 2007, 46, 4610-4613; and Decken, A., Passmore, J.,Wang, X.; Angew. Chem. Int. Ed. 2006, 45, 2773-2777.)Decamethyl-cyclopentasiloxane might also be used.

There is also a class of commercial products marketed as “lithiumsilicates”. These are generally water-based silicaceous solutions. Oneof their commercial uses is to harden and seal concrete surfaces. Theyare highly basic. An example would be LithiSil™, marketed by the PQCorporation of Valley Forge, Pa. The term “lithium silicate” in thisapplication is not used in that commercial sense. We experimented withthose commercial products and they did not generate the desiredreaction.

We also performed experiments with lithium orthosilicate, which were notsuccessful.

It was found that the treatment works better when some RF frequenciesare used as electrical stimuli than others and that the protocol yieldedheat bursts in the sealed reactor in more or less time when differentfrequencies were used as stimuli. Given how important the presence ofsilica is to the effectiveness of the treatment protocol, it isspeculated that certain natural frequencies of vibration of the silicabonds in the solution are being driven to vibrational resonance by theRF electrical stimuli, the photonic stimuli, or both. As a generalstatement, resonance is the tendency of a system or phenomena tooscillate at larger amplitude at some frequencies than others. Suchsystems and phenomena absorb energy at these resonant frequencies, suchthat stimulating a system or a phenomena at a resonant frequency or setof resonant frequencies can cause the underlying oscillation to amplify,often dramatically so. For example, the electrical stimulation maycomprise one sinusoidal signal having a frequency between 1 MHz and 20MHz added to another sinusoidal signal having a frequency between 25 MHzand 100 MHz. When viewed with an Agilent 4195A spectrum analyzer, one ofthe effective RF electrical stimuli described in the '287 patent wasshown to be a rich comb of spectra in the range of 1 MHz to 200 MHz,spaced at 6.2 MHz and having peaks in the profile of the spectral combat 3.1 MHz and 50 MHz, which were the frequencies of the underlyingpulses and the sinusoidal modulation of those pulses. That stimulusprovided literally dozens of spectra that could have been at resonantfrequencies.

Some experiments were conducted in a glass reactor of similar dimensionsto the steel one described above that permitted the reaction to beobserved as it was taking place. During the reaction, the RF stimuluswas turned off and an attempt made to capture any signals emitted by thereaction with an Agilent model DSO5054A high-speed digitizingoscilloscope. Although the emitted signals proved to be very transientand elusive, one of them was captured. It resembled a 43.4 MHz sine waveadded to a 3.1 MHz one, distorted by considerable noise. Subsequently, acleaner version of that signal generated by an Agilent 81150A waveformgenerator was used as a stimulus to the reaction. That stimulus provedto be effective.

Through experimentation, it was determined that white LEDs werenecessary to stimulate the reaction. Red and blue LEDs were used andproved not to be effective. It may be significant that white LEDsgenerate light at three frequencies.

The Specific Steps of a Representative Protocol are Shown Below:

Step 1. Prepare a solution by first adding 30 ml of heavy water (D₂O) inan open beaker. Light water (H₂O) can be used, but will have a lowerboiling point and generate a less robust reaction. Add an electrolyte of110 mg of Lithium Sulfate Monohydrate (Li₂SO₄.H₂O). Another lithium saltcould be used. Add 40 mg of lithium metasilicate (Li₂SiO₃).Alternatively, one can use an unadulterated form of anionic silicahydride in equivalent amounts, if available. Other forms of silicatesmight be used instead or in addition, such as lithium or sodiumsilicate. The solution with lithium metasilicate will be basic. Bufferthe solution with EDTA, which is a chelating agent, until it has a pHwithin the range of 6.5 to 8.9. The lithium metasilicate is only veryslightly soluble, and the EDTA serves to increase the solubility. It isnormal for some lithium metasilicate to remain suspended (i.e.,incomplete dissolution).Step 2. Immerse two or more electrodes, e.g., of palladium wire, intothe solution with sufficient spacing to avoid contact. In the case ofpalladium wire, the electrodes are preferably immersed to at least 1.0cm depth, are separated by a gap at a distance of 2.3 cm. At least oneof the electrodes will have a surface to be treated by the protocol. Theelectrode(s) to be treated are also preferably threaded with glass beadsor coated with silica to provide intimate contact with another source ofsilica.Step 3. Condition the surface of the electrodes with the followingprocess: Stimulate electrodes immersed in the liquid with electrical andphotonic stimuli while the solution is at a temperature between 90° and100° C. Stir (e.g., with a magnetic stirrer) and/or swirl gently to keepthe lithium metasilicate in suspension. The electrical stimulation maypreferably consist of a 43.4 MHz sine wave added to a 3.1 MHz one withan amplitude of 8 Volts when driven from two 50-ohm differentialoutputs. This signal was generated with an Agilent 81150A arbitrarywaveform generator. When this stimulus is applied to the electrodes, theimpedance across them will vary depending upon the characteristics ofthe solution. Simultaneously photonically stimulate the electrodes andthe gap between them using, e.g., two banks of five white “Ultrabrite”LEDs with a maximum luminous intensity of 15,000 mcd each. The LEDs arepreferably pulse-modulated by frequency-hopping through the followingsix frequencies, dwelling at each for five minutes: 464, 1234, 1289,2008, 3176, and 5000 Hz with 50% duty cycles. Continue stimulatingconcurrently with both electrical and photonic stimuli at an elevatedtemperature for fifteen minutes. After fifteen minutes, substitute a 4Volt DC stimulus for the time-varying one and apply it for five minutes.After that, re-apply the time-varying one for fifteen more minutes,followed by reversing the polarities of the DC one and applying it forfive minutes. Additionally, monitor the solution temperature with thethermocouples throughout this conditioning process to keep the solutionwithin the preferred range of 90° to 100° C.Step 4. Transfer the solution from the open beaker to a sealed reactor.The pH may have shifted during the conditioning process. If it has,buffer it with EDTA or an appropriate base (e.g., sodium bicarbonate) tobring it back into the preferred range of 6.5 to 8.9. Install theelectrodes in the reactor. Seal the reactor and introduce a blanket ofhelium and hydrogen gases above the solution to create saturation withthose gases and to maintain such saturation for the duration of theprotocol. Then heat the solution to bring it to a temperature between100° C. and 103° C. and to maintain that elevated temperature for theduration of the protocol.Step 5. Then treat the surface of the electrodes with the followingprocess: Stimulate electrodes immersed in the liquid with a time-varyingelectrical signal. The electrical stimulation may again preferablyconsist of a 43.4 MHz sine wave added to a 3.1 MHz one with an amplitudeof 8 Volts when driven from two 50-ohm differential outputs. This signalwas generated with an Agilent 81150A arbitrary waveform generator.Again, simultaneously photonically stimulate the electrodes and the gapbetween them using, e.g., the four LEDs capable of 15,000 mcd eachthrough the ports in the reactor wall described above. The LEDs arepreferably pulse-modulated by frequency-hopping through the followingsix frequencies, dwelling at each for five minutes: 464, 1234, 1289,2008, 3176, and 5000 Hz with 50% duty cycles. The four LEDs were poweredin parallel with 14.5 Volts and drew 0.02 amps each, averaged over thepulse modulation. Continue stimulating concurrently with both electricaland photonic stimuli at an elevated temperature within 2° C. of theboiling point for at least 40 minutes and preferably for two or morehours. After two hours, raise the input power to the reactor through theheating coil to increase the temperature of the solution to within 1° C.the boiling point. Additionally, monitor the solution temperature withthe thermocouples throughout the process. The surface treatment protocolshould last at least for a duration that provides some specified minimumnumber of heat bursts of at least 1° C., e.g., at least four suchbursts.

the Specific Steps of the Protocol Using Octamethylcyclo-Tetrasiloxaneare Shown Below:

Step 1: Prepare a solution by first adding 30 ml of heavy water and 110mg of Lithium Sulfate Monohydrate (Li₂SO₄.H₂O) in an open beaker. Addtwo drops of octamethyl-cyclotetrasiloxane. Heat for approximatelytwenty minutes and test the pH; the solution will be acidic and belowthe desired range for the pH. Buffer the solution with lithium hydroxideto bring into the range of 6.5 to 8.9, preferably slightly above themiddle of that range.Step 2: Place the solution in the reactor described above and place twopalladium electrodes into the solution as previously described, one ofthem being threaded with glass beads. Seal the reactor and introduce ablanket of helium and hydrogen gases above the solution to createsaturation with those gases and to maintain such saturation for theduration of the protocol. Then heat the solution to bring it to atemperature within 2° C. of the boiling point and to maintain thatelevated temperature. Monitor the solution temperature with thethermocouples throughout the process.Step 3. Then treat the surface of the electrodes with the followingprocess: Stimulate electrodes immersed in the liquid with a time-varyingelectrical signal. The electrical stimulation may again preferablyconsist of a 43.4 MHz sine wave added to a 3.1 MHz one with an amplitudeof 8 Volts when driven from two 50-ohm differential outputs. This signalwas generated with an Agilent 33250A arbitrary waveform generator.Again, simultaneously photonically stimulate the electrodes and the gapbetween them using, e.g., the four LEDs capable of 15,000 mcd eachthrough the ports in the vessel wall described above. The LEDs arepreferably pulse-modulated by frequency-hopping through the followingsix frequencies, dwelling at each for five minutes: 464, 1234, 1289,2008, 3176, and 5000 Hz with 50% duty cycles. The four LEDs were poweredwith 12.5 Volts and drew 0.02 amps each, averaged over the pulsemodulation. Continue stimulating concurrently with both electrical andphotonic stimuli at an elevated temperature within 2° C. of the boilingpoint octamethylcyclotetrasiloxane. After eight hours, raise the inputpower to the vessel to increase the temperature of the solution towithin 1° C. the boiling point. Additionally, monitor the solutiontemperature with the thermocouples throughout the process. This protocolusing octamethylcyclotetra-siloxane required the surface treatmentprotocol to last for multiple days before some specified minimum numberof heat bursts of at least 1° C. were observed.

It should be noted that this protocol with octamethylcyclotetrasiloxanewas employed in four experiments. Only two of those yielded the desiredheat transients. In contrast, the protocol with anionic silica hydrideyielded those desired heat transients in more than 90% of theexperiments.

It should also be noted that octamethyl-cyclotetrasiloxane is onlymarginally soluble. Its Material Safety Data Sheet says that its watersolubility is 0.07 g/l at 25° C., presumably in pure water. Under theconditions of the protocol above, the solubility is apparently higherthan that and sufficient to facilitate the reaction.

Three things appear to inhibit the reaction in all of the protocolsreported above: rubber, Teflon®, and ultra-pure palladium, i.e.,palladium with a purity of 99.999%. While we used Teflon® to seal thelights and electrodes, care was taken to trim it so as to minimize thesurface area exposed inside the reactor.

Here are some representative results from experiments conducted on thedates shown. The protocol evolved over time, as indicated below,culminating in the preferred protocol described above:

Dec. 28, 2008

-   -   The electrodes for this experiment were palladium in a solution        of heavy water. The electrolyte was lithium sulfate and the        silica reagent was anionic silica hydride. The time-varying        electrical stimulus was the sinusoidally modulated pulse stream        described in the aforementioned '287 patent.    -   All data logs with this application show a portion of the        complete data log, focusing on the area of interest when the        reaction was taking place. The portion of data log for the        experiment on this date is shown in FIG. 1. The time scale is        two minutes per division, as it is for all of the data logs        included with this application. Data was logged at ten second        intervals.    -   Traces 108 and 101 show the supply voltage (1V per division) and        supply current (100 mA per division) that were applied to the        heating coil for the duration of the experiment. The current is        measured as the voltage drop across a 1Ω resistor. Trace 103        records the reactor wall temperature (1° C. per division).    -   Traces 107 and 109 show the DC stimulus voltage (2V per        division) and DC stimulus current (15 mA per division), that        were applied to the electrodes for 40 minutes duration after the        baseline temperature of the solution had been reached.    -   Traces 104 and 105 record the respective temperatures (1° C. per        division) from the two thermocouples inside the beaker. The        boiling point for heavy water is 1.4° C. above that for light        water, so the baseline temperature for traces 104 and 105 is        102° C.    -   The two temperature traces 104 and 105 were observed to converge        shortly after the DC stimulus was applied, overlay tightly        (“temperature coherence”) during the stimulus, and again diverge        after the stimulus was removed. Note that at least five “bursts”        of heat were recorded by the thermocouple traces 104 and 105.        Each heat burst shows a ramp up to a peak and a nearly        symmetrical ramp down. The largest increase was a rise of        1.6° C. to 104.7° in less than four minutes.    -   The electrodes were prepared for analysis at Evans Analytical        Group in Sunnyvale, Calif. FIG. 2 is a SEM photo of the surface        of the cathode showing that some portions of it were coated with        a mat deposited from the solution used in the protocol, while        other portions were bare. From above, the deposit looked like a        field of spheres of varying sizes. From the side, it resembled a        row of teeth.    -   Spectral analyses were taken of both the deposited layer and the        bare metal, as shown in FIGS. 3 and 4. The bare metal was        revealed to be predominantly palladium, with traces of silver.        The presence of silver was not limited to a single site, but was        detected at twenty-three sites by EDS analyses of this sample.        At a later date, we cross-sectioned the same electrode and        examined its interior at several places to see if there was any        silver present. As shown in FIG. 5, there was none. We also        tested an untreated electrode from the same coil as the piece        used in this experiment for silver on its surface. There was        none. We only found silver at the surface of the treated        electrode or in the mat as discussed below.    -   We cross-sectioned the deposited mat with a Focused Ion Beam        (FIB) cut to examine the structure of the “teeth”. As shown in        FIGS. 6 and 7, they are solid rather than hollow, with some        spaces between them. In FIG. 7, one can also clearly see several        strata in the cross section. At the bottom of the picture is the        palladium electrode. Then there is a band of palladium that has        separated from the electrode and adhered to the inner surface of        the deposited mat. The SEM operator's interpretation of that        separated band is that there may have been either grain growth        or a phase change near the surface of the electrode. The mat is        at the top of the picture. The separated palladium adheres        preferentially to the mat above it and there is a very thin        stratum of lighter color at the interface of the separated        palladium and the mat where something else is going on.    -   Note that there are lighter areas between the teeth at some        points on their surfaces. Those were areas where metal was found        to be present between the teeth. The metal areas are raised        approximately 7 μm above the electrode surface. Those were areas        of metal that appeared to have seeped or wicked up between the        teeth. FIGS. 8 and 9 show a SEM photo of the metal and an EDS        spectrum taken concurrently showing that metal to consist of        both palladium and silver.    -   The verbs “to seep” and “to wick” above both imply movement by        liquids. If that is actually what is happening here, it is worth        noting that the melting point of palladium is 1555° C. The        implications are obvious; that's a very high temperature for a        reaction that is otherwise at or near the boiling point of the        solution, and it is consistent with a nuclear reaction.    -   FIGS. 8 and 9 show a SEM photo of the raised metal and an EDS        spectrum taken concurrently showing that metal to consist of        both palladium and silver. For background electron scattering,        the threshold of detection of an element is generally considered        to be 1% of the sample mass.    -   FIG. 10 is another EDS analysis of the sample. Note that it        shows the presence of fluorine. This was one of four sites that        showed fluorine to be present. We shall say more about that        below.    -   The SEM operator for most of these measurements has more than        fifteen years experience operating SEM equipment. Although the        EDS spectra lines of palladium and silver are close to each        other, in his opinion, the presence of the silver was        “irrefutable”. This palladium electrode was never used as the        cathode with a silver anode.

Jan. 3, 2009

-   -   The electrodes for this experiment were palladium in a solution        of heavy water. The electrolyte was lithium sulfate and the        silica reagent was anionic silica hydride. The time-varying        electrical stimulus was the sinusoidally modulated pulse stream        described in the aforementioned '287 patent.    -   The purpose of the experiment was to create a sample for Auger        and Raman testing of its surface.    -   The data logs are shown in FIG. 11. Although we didn't see the        temperature coherence observed in other experiments, there were        some distinct bursts of energy. They were broader and less        abrupt than in some other experiments. One of the two        thermocouples recorded a burst that rose almost 4° C. and lasted        fourteen minutes. Note also that the final burst of heat        occurred after the input power to the heating coil was secured.    -   The summary report from the Auger analysis is shown in FIG. 12.        We will discuss it further below.    -   The Raman testing showed lithium sulfate on the surface, which        was washed away when the sample was rinsed with distilled water.        Curiously, the analysis did not show the presence of silica,        suggesting, according to the operator, that it was either “not        present, or because it was a disordered amorphous SiO_(x)        compound that was not able to produce Raman spectra”.    -   Subsequent EDS testing of this sample did not show evidence of        silver in the palladium, but that may only mean that it was not        present in sufficient amounts to rise above the 1% detection        threshold of sample mass discussed above.

Jan. 19, 2009

-   -   The experiment was conducted with palladium electrodes in heavy        water. The electrolyte was lithium sulfate and the silica        reagent was anionic silica hydride. The time-varying electrical        stimulus was the sinusoidally modulated pulse stream described        in the aforementioned '287 patent.    -   The data log in FIG. 13 shows replication of the bursts of heat,        as seen by the thermal signatures of the recorded temperatures        (traces 204 and 205). These bursts had exceptional periodicity,        occurring at intervals of approximately thirteen minutes.    -   Note that the temperatures of the heating coil (trace 202) and        the reactor wall (trace 203) drop after each burst, possibly        caused by one or both of the relief valves lifting and venting        some steam. Although the reactor was not observed directly        during any of these experiments because it was enclosed within        an insulated box for safety reasons, venting through the relief        valves would be consistent with the loss of approximately        one-third of the liquid in the reactor during the experiment.    -   Note also that the DC stimulus current (trace 209) spikes        concurrent with or slightly before the bursts occur. Those        current spikes suggest that the resistance between the DC anode        and the common cathode decreased at the same time the        temperature spikes were occurring. (We logged the DC stimulus        voltage and current for most of the experiments. Current        variations were seen in some other cases, but not as large as        those shown here.)    -   FIG. 14 is included to show the one of the EDS results from the        cathode in this experiment. We did not find silver on these        samples, but note the presence of aluminum. We will say more        about that below.

Jan. 30, 2009

-   -   The electrodes for this experiment were palladium in a solution        of heavy water. The electrolyte was lithium sulfate and the        silica reagent was anionic silica hydride. The time-varying        electrical stimulus was the sinusoidally modulated pulse stream        described in the aforementioned '287 patent.    -   This experiment featured four small glass beads threaded onto        the cathode. For example, Hirschberg Schutz & Co., Inc., of        Warren, N.J., markets such beads. The glass beads used in this        experiment proved to have been coated with pure silver by the        manufacturer. The manufacturer makes other glass beads that are        not coated, and we used those in later experiments.    -   The data log for the experiment is shown in FIG. 15. The        reaction commenced at a relatively low temperature (baseline        temperature just above 100° C.) and showed some sustained bursts        lasting as long as five minutes. The temperature of the solution        (traces 304 and 305) peaked at 102.4° C. Note that the        temperature spikes last longer than the ones in the previous        tests, corresponding to more heat being generated with the        threaded beads than with bare electrodes. There is a strong        reaction before the DC stimulus voltage (indicated by trace 307)        was even applied, indicating that the DC stimulus is optional in        the protocol. For that reason, we only used two electrodes, the        RF anode and the cathode, in most of our later experiments.    -   When viewed in the SEM with the glass beads removed, there were        no deposits on this electrode and significant portions of the        electrode had spalled and peeled away, again providing evidence        of local high temperatures. FIG. 16 shows a piece of the        electrode that has been twisted, as though by extreme heat. FIG.        17 shows a small piece of palladium that was smooth on one side        and textured on the other. The textured side does not appear to        be the result of shear or etching, and it may have been melted.        If that is verified with additional experiments, it will be very        significant because it would confirm that, with the bead        covering, the electrode attained melting temperature (1555° C.        for palladium).    -   We found numerous Pd fragments had adhered to the surface of the        beads. One site was seen that was predominately palladium, with        silver present in trace amounts.    -   It should be noted that spalling was observed in several        experiments where glass beads were threaded on an electrode. It        was not observed on electrodes which did not have glass beads        threaded, thus indicating that the physical contact between the        electrode and the glass caused the spalling.

Feb. 21, 2009

-   -   The electrodes for this experiment were palladium in a solution        of predominately light water. The electrolyte was lithium        sulfate and the silica reagent was anionic silica hydride. The        time-varying electrical stimulus was the sinusoidally modulated        pulse stream described in the aforementioned '287 patent. (The        citric acid solution added to balance the pH in this experiment        was made with heavy water. Because less than four drops were        added into 30 ml of solution, we describe the water as being        “predominately” light.)    -   Glass beads were threaded onto the electrode as described above.    -   Because the boiling point of light water is lower than for heavy        water by about 1.4° C., the temperatures were deliberately kept        lower for this experiment to stay just below the lower boiling        point.    -   The data log for the experiment is shown in FIG. 18. Although        the temperatures recorded are lower than those in the previous        experiments with heavy water, the centerline for the two traces        (404 and 405) show the temperature of the solution is still        102° C. There were definite bursts of energy recorded in the        data logs in the now-characteristic thermal signature, although        they were not as regular or robust as the experiments using        heavy water. The temperatures of the heating coil (trace 402)        and the reactor wall (trace 403) drop with the bursts of heat,        again suggesting that the relief valves have lifted.

Feb. 28, 2009

-   -   The electrodes for this experiment were silver in a solution of        heavy water. The electrolyte was lithium sulfate and the silica        reagent was anionic silica hydride. The time-varying electrical        stimulus was the sinusoidally modulated pulse stream described        in the aforementioned '287 patent.    -   As shown in FIG. 19, there were again several distinct bursts of        heat (traces 504 and 505) that included the “temperature        coherence” observed with the palladium electrode.    -   The electrodes were tested with SEM and EDS. The silver proved        to have been corroded by the treatment. However, the presence of        fluorine was detected at four sites.    -   The significance of these results is that the contemporary model        regarding LENRs observed in similar electrolytic cells requires        palladium. The crystal lattice of palladium is spacious enough        to absorb both hydrogen and deuterium atoms, thus holding them        in proximity. That model further hypothesizes that this        containment permits adjacent deuterium atoms to interact in ways        that are not otherwise stochastically possible at low        temperatures. These assumptions then imply an interaction that        is believed to permit the deuterium nuclei to get close enough        to each other that they fuse. The protocol described in the        patent referenced above and the present application does not        depend upon that model. Silver does not absorb either hydrogen        or deuterium atoms, so something is happening in the protocol        described herein that must follow a completely different model.        We did not measure the D/Pd atom ratio, so there is no such        experimental evidence to report in that regard.

Mar. 5, 2009

-   -   The electrodes for this experiment were platinum in a solution        of heavy water. The electrolyte was lithium sulfate and the        silica reagent was anionic silica hydride. The time-varying        electrical stimulus was the sinusoidally modulated pulse stream        described in the aforementioned '287 patent.    -   As shown in FIG. 20, there were several distinct bursts of heat        (seen in traces 604 and 605), although the recorded temperatures        did not demonstrate the “temperature coherence” observed with        the palladium and silver electrode. The bursts of heat showed a        periodicity of approximately six minutes. Of particular interest        is the fact that after the input power to the reactor (traces        601 and 608) and the stimuli were secured (right side of the        data log), the temperature of the solution continued to rise for        more than eight minutes while the temperature of the heating        coil (trace 602) and the reactor sidewall (trace 603) fell.        Clearly, there was some delayed exothermic reaction occurring        inside the reactor.    -   The cathode from this experiment was examined with SEM and EDS.        The surface of the electrode was clean rather than corroded as        the silver had been. No transmutation products were detected.        Again, that may only mean that they were present, but not in        sufficient amounts to rise above the 1% detection threshold.    -   As above with silver, according to the contemporary model for        LENRs, there should not have been any evidence of heat because        of the size of the platinum crystal lattice.

Aug. 9, 2009

-   -   In an effort to test whether the anionic silica hydride and        lithium sulfate in the solution were reacting to produce a form        of lithium silicate, we substituted reagent grade lithium        metasilicate, Li₂SiO₃, for the anionic silica hydride. Because        lithium metasilicate is essentially insoluble in water, it        settled immediately to the bottom of the beaker without        dissolving. We therefore used EDTA, a chelating agent, to get        some of the lithium metasilicate to dissolve or suspend in the        water.

Specifically, we made a solution consisting of 30 ml of D2O, 350 mg ofLi₂SiO₃, 850 mg of Li₂SO₄, and 700 mg of EDTA. That formed a cloudysolution, suggesting that the Li₂SiO₃ was either in solution orsuspension. EDTA is acidic, so we buffered the solution with sodiumbicarbonate, NaHCO₃, to bring it back into the pH range called for inthe protocol. After heating and stirring, we added another 350 mg ofEDTA and buffered again with NaHCO₃. The electrodes were palladium.

-   -   The data log for this experiment is shown in FIG. 21. The        boiling point of this solution was higher than that in the        standard protocol, so the centerline of the two traces (704 and        705) for the thermocouples is 104° C. There were some bursts of        heat, but they were not periodic. One of those bursts was almost        1° C. in less than ten seconds.    -   The electrodes used in this experiment were later analyzed with        SEM and EDS. There was a coating on the cathode that included        carbon, oxygen, sodium, silicon, and sulfur. The coating was not        as well organized as that shown on some of the earlier SEMS.    -   The pH of the solution at the beginning of the experiment was        7.45. At the end, it was 9.70, so it is apparent that some        chemical reaction took place in the solution during the course        of the experiment.

Aug. 15, 2009

-   -   In a further effort to confirm that silica was a critical part        of the protocol, we conducted another experiment with 30% sodium        silicate (“water glass”), Na₂SiO₃, as the source of the        silicate. Na₂SiO₃ is readily soluble in water, producing an        alkaline solution. The sodium silicate tended to congeal at        higher temperatures, so we finally used only one drop of it in        30 ml. of heavy water. The other ingredients were 350 mg of        Li₂SO₄ and 150 mg of EDTA. This yielded a highly acidic solution        that we again buffered into the desired range of 6.9 to 8.9 with        sodium bicarbonate. The electrodes were palladium, and the        time-varying electrical stimulus was the sinusoidally modulated        pulse stream described in the aforementioned '287 patent.    -   A portion of the data log for this experiment is shown in        FIG. 22. Again, the centerline for the thermocouple traces (804        and 805) was 104° C., because the boiling point of this solution        was higher than that of the solution in the standard protocol.        There were a small number of bursts of heat during the        experiment. These heat bursts were rather feeble, but        nevertheless were present.    -   A SEM photo and the accompanying EDS spectrum are shown in        FIG. 23. Note the presence of magnesium, which could either be a        transmutation product of sodium or a contaminant. We did not        test the raw materials in this experiment for contaminants.

Nov. 15, 2009

-   -   The electrodes for this experiment were palladium in a solution        of heavy water. The electrolyte was lithium sulfate and the        silica reagent was lithium metasilicate, Li₂SiO₃. The        time-varying electrical stimulus was the sinusoidally modulated        pulse stream described in the aforementioned '287 patent.    -   This was a version of the protocol intermediate between the one        described in the described in the '287 patent and the one        described above.    -   The cell began to respond much more rapidly than previous        experiments. FIG. 24 shows the data log for this experiment. The        pulses of heat were not very large, but there were many of them,        and they tended to repeat every three to five minutes.    -   The electrodes from this experiment were analyzed with SEM and        EDS. They proved to be relatively clean and showed no evidence        of transmutation products.

Dec. 31, 2009

-   -   The electrodes for this experiment were palladium in a solution        of heavy water. The protocol in this experiment was the one        described above as the preferred embodiment of the invention.        This experiment included glass beads on one of the electrodes;        these beads were not coated in silver.    -   The data logs of the experiment are shown in FIG. 25. Some        smaller burst of heat had preceded the portion of the data log        shown in that figure. The large burst shown in the figure raised        the temperature reading of one of the thermocouples by        approximately 2° C. in twenty seconds and lasted more than six        minutes.    -   FIG. 26 shows a site in a SEM photo of one of the palladium        electrodes from this date. Lighter areas are radiating from a        central point. There was no difference between the lighter areas        and the neighboring surface in EDS analysis. This was one of        several sites with a similar appearance on this sample that show        what could be ejecta from a localized burst of heat on the        electrode.    -   There is also a piece of electrode that has separated at the        right side of the photo. It partially covers a deposit of        sulfate that was laid down during the protocol, indicating that        the separation occurred during or after the protocol. There is        no indication that mechanical action caused the separation, so        it may have been caused by thermal stresses.    -   Note that if there was a localized burst of heat on the        electrode sufficient to melt, or even to vaporize, the        palladium, it would also be intense enough to vaporize the water        in the immediate vicinity, forming a burst of steam. That burst        of steam would expand out from the origin of the heat in a        compression shock wave until it lost heat to the surrounding        solution. At some point it would collapse back upon the center.        When the bubble collapsed back, it could press the ejecta back        upon the surface of the electrode in the manner shown in the        picture.    -   Roger Stringham has reported on Pd/D₂O cavitation experiments        that yield transient bubbles in such a manner. He has shown that        the bubble originates in a fusion event within a palladium        lattice and contains D₂O, D₂, and O₂ and describes the dynamics        of the high-energy transient bubbles in detail. H is report can        be found at this URL:        http://www.lenr-canr.org/acrobat/StringhamRcavitationb.pdf.    -   We rinsed the electrode tested above in distilled water to        remove the sulfate and re-examined it. The later testing did not        show pore sites of ejecta and the radial patterns were no longer        visible.

Dec. 15, 2013

-   -   This was the third day of an experiment using palladium        electrodes in a solution of heavy water, lithium silicate, and a        siloxane. The protocol in this experiment was the one described        above for octamethylcyclotetrasiloxane. This experiment included        glass beads on one of the electrodes.    -   The data logs of the experiment are shown in FIG. 27. Some        smaller burst of heat had preceded the portion of the data log        shown in that figure. The large burst shown in the figure raised        both of the thermocouples approximately 1.4° C. in twenty-five        seconds and lasted several minutes.    -   Note that FIG. 27 includes a temperature trace not shown in        earlier data logs. That trace shows the temperature in the        headspace above the liquid surface in the reactor. It closely        tracks the two temperatures recorded in the liquid, thus        indicating that the entire volume of the reactor is experiencing        a simultaneous increase.

Taken together, we believe the experiments conducted with anionic silicahydride, lithium metasilicate, sodium silicate, and siloxane support thereasoning that silica is critical to the reaction and that a lithiumsilicate promotes a stronger reaction.

One of the things that caught our attention in the experiments above wasthe frequent indication of fluorine in the EDS analyses. The Feb. 28,2009, experiment showed F at four sites. Several samples showed tracesof aluminum and one showed gallium at multiple sites. Flanagan's anionicsilica hydride includes several additives. H is “Mega H-™” powdercontains potassium citrate (K₃C₆H₅O₇), potassium carbonate (K₂CO₃), andoleic acid (C₁₈H₃₄O₂). H is “Super Hydrate™” solution also containspotassium carbonate and oleic acid, plus magnesium sulfate (MgSO₄). Wetested Flanagan's products with EDS analysis to clarify their elementalcomposition. Sodium and copper were found to also be present, althoughthey were not disclosed as ingredients on the product labels. Lithiumsulfate (Li₂SO₄) is used in our protocol as an electrolyte. However, theidentified original ingredients for the protocol do not account for thepresence of fluorine, aluminum and gallium in the post-experiment EDSanalyses.

Now return to FIG. 12, the Atomic Concentration Table from the Augeranalysis of the Jan. 3, 2009 experiment. Note the presence of nitrogen,aluminum, chlorine, calcium and zinc. Each of these could be atransmutation product of one of the elements added to the reactor,assuming those elements undergo Beta decay or a reaction similar to Betadecay. Specifically:

-   -   ₆C transmutes into ₇N    -   ₁₂Mg transmutes into ₁₃Al    -   ₁₆S transmutes into ₁₇Cl    -   ₁₉K transmutes in ₂₀Ca    -   ₂₉Cu transmutes into ₃₀Zn

Further, the ₉F found above in the EDS analyses is the transmutationproduct of ₈O.

If hydrogen or lithium had transmuted to helium and beryllium, EDS wouldnot have detected them, because it does not detect elements with atomicnumbers below five.

The gallium in the various samples is an escape peak of palladium inEDS, so it can be dismissed as a false positive for that element.

We now have found strong evidence of transmutation products of sixdifferent elements using two different techniques for elementalanalysis, with aluminum having been found with both of them. Takentogether, the data supports a claim that our protocol has inducednuclear reactions on numerous occasions. While that claim will doubtlessbe controversial, we assert that the evidence for it is strong.

Further, we calculated the energy density of one of the reactions loggedon Dec. 31, 2009, assuming the active region of the reaction detectedwas within 7 μm of the surface of the electrode. That is consistent withthe visual evidence in the SEM image shown in FIG. 6, where the metalhas coated the interior surfaces of the deposited mat.

Energy density is the energy per unit volume or mass. The temperatureincrease during the first 20 seconds of the temperature pulse shown inFIG. 21 averaged 1.86° C. Raising 30 ml of water that much requiresapproximately 56 calories. This converts to 234 joules in SI units.

Given that the electrodes have a diameter D of 0.063 mm and that theyare immersed to a depth 1 of 15 mm in the solution, the volume of theactive region of the two electrodes can be calculated with the formulabelow, which approximates the formula for the volume of a hollowcylinder:

$\begin{matrix}{V = {\pi \times D \times 1 \times 2}} \\{= {3.14 \times {.063}\mspace{14mu} {mm} \times 15\mspace{14mu} {mm} \times 7\mspace{14mu} {µm} \times 2}} \\{= {41.5\mspace{14mu} 10^{- 12}\; m^{3}}}\end{matrix}$

The energy density of the reaction shown in the data log is thus 234Joules/41.5×10⁻¹² m³ or 5.64×10³ MJ/L.

Making the worst-case assumption that the active region of the reactionhas the 12.0 g/cm³ density of fully dense palladium, that converts to470 MJ/kg.

That energy density is several times greater than molecular energydensities, thus providing further evidence that the reaction is not amolecular chemical reaction.

At the present state of the research in LENRs, it is not known whetherthe lithium silicate is a reactant, in which case it would be consumedin the reaction, or a catalyst, in which case it would not be consumed.

The nature and shape of the bursts of heat recorded in our data logs,together with the condition of the electrode surfaces seen from SEManalyses, indicate that the surface temperature of the electrodes maylocally approach or even attain the 1555° C. melting point of palladium,such that the solution at the surface of that electrode can locallyflash to steam. A continuous reaction requires the on-goingreplenishment of solution in the liquid phase, which naturally occurs inthe test reaction reactor. An alternative protocol may be to providefresh solution at that inlet of a nozzle where the steam is exhausted.

There is no evidence in any of our experiments that the exothermicreaction being induced is anything other than a surface effect. Giventhe apparent energy densities of that reaction, that could be veryimportant because it indicates that, for whatever reason, the reactionis self-limiting to the surface area of the electrodes.

Finally, we note that the concept of “boiling point” is ambiguous insidea sealed reactor. If the reactor is perfectly sealed, the pressureinside the reactor will increase with temperature to a point that isequal to the vapor pressure of the water. We found over time, that ourreactor was not perfectly sealed by conducting leak tests. It isdifficult to seal such a reactor if one is denied the use of rubber andTeflon™ for gaskets, and we had wanted to avoid rubber and minimizeTeflon since they appear to inhibit the reaction, as noted above.

This suggests a possible model for the reaction detected in ourexperiments where a slight leak might have momentarily lowered thepressure within the reactor and allowed steam bubbles to form on anelectrode. Those bubbles might be the site of the reaction, and the heatfrom an initial spark of such a reaction could cause a cascadingreaction, which would quench when the reactor regained its seal.

Over a period of several months, we improved the seal of the reactor.Over that period, we also noted that the temperature spikes becamesmaller. Where increases of almost 2 degrees C. had been common, werarely saw increases much greater than 1 degree C. That suggests that asuperior seal might be undesirable if the reaction is occurring in thesolution at the locus of phase change.

Others attempting to reproduce our results should be alert to thepossibility the reaction occurs at the phase change interface of waterand steam. Accordingly, they may want to try experiments with andwithout a very slight leakage.

We have use the term “boiling point” in the protocols above to mean theboiling point of the solution at standard atmospheric pressure.

What is claimed is:
 1. A method of preparing materials at or near theirsurfaces, comprising: preparing a solution including a lithium silicate,in a liquid; heating and maintaining the solution at an elevatedtemperature to within 5° C. of the boiling point in a sealed reactor;photonically stimulating the solution with illumination from a lightsource; and electrically stimulating two or more conductive electrodesimmersed within the solution over an extended time period by applying avoltage between electrodes such that an exothermic reaction occursevidenced by measured temperature increases during such electrical andphotonic stimulating, at least one of the electrodes having a surface tobe treated thereby and in intimate contact with a source of silicaceousmaterial, wherein at least one electrode being treated experiences localvaporization of the solution.
 2. The method as in claim 1, wherein theliquid for the solution comprises water.
 3. The method as in claim 2,wherein the water is predominantly light water (H₂O).
 4. The method asin claim 2, wherein the water is a combination of light water (H₂O) andheavy water (D₂O).
 5. The method as in claim 2, wherein the water ispredominantly heavy water (D₂O).
 6. The method as in claim 1, wherein asurfactant is added to the solution.
 7. The method as in claim 1,wherein a buffering agent is added to the solution so as to maintain apH in a range from 6.5 to 8.9.
 8. The method in claim 1, wherein thesolution in the sealed reactor is heated above its boiling point atatmospheric pressure and its pressure rises above one standardatmosphere.
 9. The method as in claim 1, wherein the sealed reactorcomprises a glass- or silica-lined vessel with ports for the electrodesand for one or more thermocouples.
 10. The method as in claim 1, whereinthe solution in the sealed reactor is blanketed with a gas.
 11. Themethod as in claim 10, wherein the gas comprises hydrogen, helium, or acombination thereof.
 12. The method as in claim 10, wherein the solutionis saturated with the blanketing gas.
 13. The method as in claim 1,wherein the sealed reactor is lined with a piezoelectric material. 14.The method as in claim 13, wherein the piezoelectric material is aporcelain glaze.
 15. The method as in claim 1, wherein the light sourceproviding the photonic stimulation of the solution comprises a set ofmodulated light emitting diodes.
 16. The method as in claim 15, whereinthe light emitting diodes are white.
 17. The method as in claim 1,wherein the electrical and photonic stimulation are provided over anextended time period of at least 40 minutes.
 18. The method as in claim1, wherein the solution includes at least one electrolyte other thanlithium silicate.
 19. The method as in claim 18, wherein the electrolytecomprises a lithium salt.
 20. The method as in claim 19, wherein thelithium salt comprises lithium sulfate (Li₂SO₄).
 21. The method as inclaim 1, wherein at least one of the electrodes is coated withsilicaceous material.
 22. The method as in claim 1, wherein a source ofthe silicaceous material in contact with the electrodes comprises asilica compound in suspension in the water.
 23. The method as in claim22, wherein a chelating agent facilitates the suspension of the silicacompound.
 24. The method as in claim 23, wherein the chelating agent isEDTA.
 25. The method as in claim 1, wherein a source of the silicaceousmaterial in contact with the electrodes comprises a silica compound insolution.
 26. The method as in claim 25, wherein the silica compound insolution comprises a silsesquioxane composition.
 27. The method as inclaim 26, wherein the silsesquioxane composition comprises anionicsilica hydride.
 28. The method as in claim 1, wherein a source of thesilicaceous material comprises one or more silica or glass beadsthreaded over the one or more electrodes being surface treated.
 29. Themethod as in claim 1, wherein a source of silicaceous material lieswithin the composition of the electrode.
 30. The method as in claim 29,wherein a source of silicaceous material comprises an electrodeconsisting of sintered metal and silica.
 31. The method as in claim 1,wherein a source of silicaceous material includes a silica or glasslining of the sealed reactor.
 32. The method as in claim 1, wherein thelithium silicate is introduced into the reactor as an initialingredient.
 33. The method as in claim 1, wherein the lithium silicateis a reaction product of initial ingredients of preparing the solution.34. The method as in claim 1, wherein the lithium silicate comprises asilicaceous ring molecule with a lithium ion contained within the ring.35. The method as in claim 1, wherein the lithium silicate comprises asilicaceous cage molecule with a lithium ion contained within the cage.36. The method as in claim 1, wherein the conductive electrodes aremetal.
 37. The method as in claim 36, wherein the metal comprises one ormore of palladium, silver, platinum and gold.
 38. The method as in claim36, wherein the conductive electrodes are of the same metal.
 39. Themethod as in claim 36, wherein the conductive electrodes are ofdissimilar metals.
 40. The method as in claim 1, wherein at least one ofthe electrodes is a conductive material other than metal.
 41. The methodas in claim 1, wherein the electrical and photonic stimuli are appliedconcurrently.
 42. The method as in claim 1, wherein the electrical andphotonic stimuli are applied sequentially.
 43. The method as in claim 1,wherein the electrical stimulation comprise a complex RF signal with atleast some spectral components coinciding with molecular vibrationalresonance frequencies in the solution.
 44. The method as in claim 1,wherein the electrical stimulation comprises a sinusoidal signal have afrequency between 1 MHz and 20 MHz added to another sinusoidal signalhaving a frequency between 25 MHz and 100 MHz.
 45. The method as inclaim 1, wherein the electrical stimulation is a direct current voltage.46. The method as in claim 1, wherein the electrical stimulation is analternating current voltage.
 47. The method as in claim 46, wherein thealternating current voltage has frequencies in the RF range.
 48. Themethod as in claim 47, wherein the alternating current voltage hasfrequencies coinciding with absorptive spectra of components in thesolution.
 49. The method as in claim 1, wherein the electricalstimulation comprises a replication of an electrical waveform emittedduring a desired exothermic reaction.
 50. The method as in claim 1,wherein the electrical stimulation is a direct current voltage and analternating current voltage applied concurrently between separate anodesand a common cathode.
 51. The method as in claim 1, wherein theelectrical stimulation is a direct current voltage and an alternatingcurrent voltage applied concurrently between a common anode and a commoncathode.
 52. The method as in claim 1, wherein the electricalstimulation is a direct current voltage and an alternating currentvoltage applied sequentially between separate anodes and a commoncathode.
 53. The method as in claim 1, wherein the electricalstimulation is a direct current voltage and an alternating currentvoltage applied sequentially between a common anode and a commoncathode.
 54. The method as in claim 1, wherein the light sourceproviding the photonic stimulation of the solution is modulated.
 55. Themethod as in claim 54, wherein the light source is square-wavemodulated.
 56. The method as in claim 54, wherein the light source ispulse-modulated.
 57. The method as in claim 54, wherein the light sourceis modulated with a frequency that varies or hops.